Polycarboxylic acid esters of oxypropylated alkyl monoamines



Unite POLYCARBOXYLIC ACID ESTERS OF OXYPRO- PYLATED ALKYL MONOAMINES No Drawing. Application April 10, 1952, Serial No. 281,652

12 Claims. (Cl. 260-475) The present invention is concerned with certain new chemical products, compounds, or compositions which have useful application in various arts. It includes methods or procedures for manufacturing said new chemical products, compounds or compositions, as well as the products, compounds, or compositions themselves.

The present invention is concerned with fractional esters obtained from a polycarboxy acid or the equivalent and oxypropylation derivatives in turn from the oxypropylation of high molal amines in which there is present at least one radical having not less than 8 and as many as 32 uninterrupted carbon atoms in a single group. Many of these amines are conveniently obtained from higher fatty acids or other similar detergent-forming acids. Actually the hydrocarbon group may be modified by the presence of a hydroxyl group as, for example, an amine obtained from ricinoleic acid, hydroxystearic acid, etc. The presence of such hydroxyl radical, or the equivalent, in no way detracts from the suitability of the amine. Not only can the amines be obtained from fatty acids but also can be obtained from high molal carboxy acids such as abietic acid, naphthenic acid, acids obtained by the oxidation of petroleum, etc. Obviously, when obtained from fatty acids there is no need to separate the original fatty acids as they occur in nature in the form of glycerides. Thus, such aliphatic amines may represent a mixture of more than one acid, particular reference being to high molal aliphatic amines which are primary amines and in which the carbon atom chain has 8 to 18 carbon atoms. These are designated generally as octylamine, decylamine, hexadecylamine, etc. The amines may contain an unsaturated group as in the case of octadecadienyl amine. The amine need not be monoamino but may be polyamino as is the case with certain amines offered in the open market, such as Duomeen T manufactured by Armour & Company and described in a pamphlet entitled Duomeens. Actually, any of the selected amines can be readily converted into a polyamine by merely reacting with an imine, such as ethylene imine, propylene imine, etc. One may also convert a monoamine or, for that matter, a polyamine, into a compound containing at least one more nitrogen atom by means of reactants which contain not only at least one nitrogen atom but contain additionally a 1,2 epoxy ring, such as those described in U. 5. Patents Nos. 1,977,251, dated Oct. 16, 1934, to Stallmann; 1,977,253 dated Oct. 16, 1934 to Stallmann, and 2,520,093 dated Aug. 22, 1950, to Gross. From a standpoint of effectiveness in demulsification and also from a standpoint of economy I have found it most advisable to use the monoamines and particularly an aliphatic amine having at least one radical containing 12 to 18 carbon atoms in the aliphatic chain.

As three specific examples of particularly suitable initial reactants I direct attention to the dodecylamine sold by Armour Chemical Division, Armour and Company, under the trade name Armeen 12. This particular product carries about 90% dodecylamine, 9% tetradecylamine, and 1% octadecenylamine. Another equally satisfactory @ECHK 2,7 14,611 Patented Aug. 2, 1955 market, such as those previously described, and subject them to alkylation with conventional reactants such as dimethyl sulfonate, etc. etc., so as to introduce an alkyl group or an arylalkyl group' as in the case of benzyl chloride. The resulting product is a secondary amine containing one long chain of 8 carbon atoms or more, and one short chain having less than 8 carbon atoms in its length. One also can purchase secondary amines having two long chains in which each alkyl radical has at least 8 carbon atoms or more. Although, such secondary amines can be subjected to oxypropylation as herein described, it is my preference to convert these secondary amines, having two alkyl radicals as described, into products which are susceptible to oxypropylation at more than one. point, i. e., have present two or more reactive hydroxyl radicals. The procedure involves nothing more than what is well known, i. e., an oxyalkylation procedure involving at least one mole, and if desired two or three moles of glycide, per mole of secondary amine. For practical purposes I have found that one mole of glycide per mole of secondary amine, yielding a tertiary amine having two reactive hydroxyl radicals, serves as a very suitable material for oxypropylation and esterification of the oxypropylated derivative as described subsequently.

The amine employed preferably has present a basic nitrogen atom as in the high molal aliphatic amines previously mentioned. However, this need not be the case as, for example, in the instance of a substituted phenylamine, such as butylphenylamine, i. e., aniline with a ring substituent having two or more carbon atoms. The nitrogen, of course, in this instance is either not basic at all or only weakly basic.

As to patents which show one or more amines suitable for the instant purpose, reference is made to U. S. Patents Nos. 2,304,805, dated Dec. 15, 1942, to Denman; 2,334,517, dated Nov. 16, 1943, to Tucker; and 2,363,- 923, dated Nov. 28, 1944, to Denman.

Attention is directed to U. S. Patent No. 2,562,878, dated August 7, 1951, in which there is described, among other things, a process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of an esterification product of a dicarboxylic acid and a polyalkylene glycol, in which the ratio of equivalents of polybasic acid to equivalents of polyalkylene glycol is in the range of 0.5 to 2.0, in which the alkylene group has from 2 to 3 carbon atoms, and in which the molecular weight of the product is between 1,500 to 4,000.

In the instant case the initial starting materials, i. e., high molal amines, are oil-soluble. In other words, in addition to any other requirements hereinafter noted the amines used as raw materials must be soluble in oil or in a non-hydrophile solvent such as xylene.

Numerous water-insoluble compounds susceptible to oxyalkylation, and particularly to oxyethylation, have been oxyethylated so as to produce effective surface-active agents, which, in some instances at least, also have had at least modest demulsifying property. Reference is made to similar monomeric compounds having a hydrophobe group containing, for example, 8 to 32 carbon atoms and a reactive hydrogen atom, such as the usual acids, alcohols, alkylated phenols, amines, amides, etc. In such instances, invariably the approach is to introduce a counterbalancing effect by means of the addition of a hydrophile group, particularly ethylene oxide or, in some instances, glycide, or perhaps a mixture of both hydrophile groups and hydrophobe groups, as, for example, in the introduction of propylene oxide along with ethylene oxide. On another type of material a polymeric material, such as resin, has been subjected to reaction with alkylene oxides including propylene oxide. In such instances certain derivatives obtained from polycarboxy acids have been employed.

Exhaustive oxypropylation renders a water-soluble material water-insoluble. Similarly, it renders a keroseneinsoluble material kerosene-soluble; for instance, reference has been made to the fact that this is true, for example, using polypropyleneglycol 2,000. Actually, it is true with polypropyleneglycol having lower molecular weights than 2,000. These materials are obtained by the oxypropylation of a water-soluble kerosene-insoluble material, i. e., either water or propyleneglycol.

Obviously, in light of what has been said the selected raw materials are not necessarily limited to those having two labile hydrogen atoms as in the case of an ordinary high molal aliphatic primary amine but there may be present a number of points of reaction such as polyarnines of the kind indicated, i. e., obtained by the treatment of ethylene imine. Needless to say, oxypropylation of such amines will not yield a diol but will yield polyols or the equivalent in which there may be present 3, 4, or even more hydroxyl radicals. However, my preferred reactants are primary amines which on oxypropylation will yield diols or the equivalent, i. e., a product having two terminal hydroxyl radicals.

Generally speaking, I prefer to use approximately 4 to 10 moles of propylene oxide per labile hydrogen atom. For instance, in the case of the primary aliphatic amines above referred to my preference is to use 8 to 20, and particularly 14 to 20, moles of propylene oxide per mole of amine. In other instances 1 have obtained excellent results using up to 40 moles of propylene oxide. The fact that these products yield surface-active agents effective for various purposes and particularly for demulsification at a low stage of oxypropylation compared with higher oxypropylated products, for example, with castor oil, as described in my co-pending application, Serial No. 281,- 648, filed April 10, 1952, now U. S. Patent 2,695,909, is unexplainable.

In any event, having obtained oxypropylated derivatives of the kind above noted and hereinafter described in greater detail the next step is treatment with the polycarboxy acid, particularly a dicar'ooxy acid, so as to produce a fractional ester. The amount of polycarboxy acid, such as phthalic acid or anhydride, maleic acid or anhydride, diglycolic acid, etc., is equivalent to one mole of the polycarboxy acid for each available hydroxyl radical.

Thus, the present invention is concerned with hydrophile synthetic products; said hydrophile synthetic products being the acidic fractional esters derived by reaction between (A) a polycarboxy acid, and (B) high molal oxypropylation derivatives of amines having present at least one group in which there is present at least 8 and not more than 32 carbon atoms, with the proviso that (a) the initial amine be xylene-soluble; (b) the amount of propylene oxide employed be not less than 4 and not over 20 moles per reactive hydrogen atom present in the original amine including reactive hydrogen atoms attached to an oxygen atom; (c) the oxypropylation product must be xylene-soluble; and with the further proviso that the ratio of (A) to (B) be one mole of (A) for each hydroxyl radical present in (B).

As previously pointed out it is my preference that the initial amino reactant selected contain an aliphatic chain having 12 to 18 carbon atoms and be monoamino in character. Furthermore, I prefer that the amine be a primary amine and that the amount of propylene oxide employed be 8 to 20 moles per mole of amine.

Although the herein described products have a number of industrial applications, they are of particular value for resolving petroleum emulsions of the water-in-oil type that are commonly referred to as cut oil, roily oil," emulsified oil, etc., and which comprise fine droplets of naturally-occurring waters or brines dispersed in a 7 more or less permanent state throughout the oil which constituted the continuous phase of the emulsion. This specific application is described and claimed in my copending application, Serial No. 281,651, filed April 10, 1952.

The new products are useful as wetting, detergent and leveling agents in the laundry, textile and dyeing industries; as wetting agents and detergents in the acid washing of building stone and brick; as wetting agents and spreaders in the application of asphalt in road building and the like; as a flotation reagent in the flotation separation of various aqueous suspensions containing negatively charged particles, such as sewage, coal washing waste water, and various trade wastes and the like; as germicides, insecticides, emulsifying agents, as, for example, for cosmetics, spray oils, water-repellent textile finishes;

' as lubricants, etc.

For convenience, what is said hereinafter will be divided into four parts:

Part 1 will be concerned with the oxypropylated derivatives obtained from the previously described amines;

Part 2 will be concerned with the preparation of esters from the hydroxylated products, and particularly dihydroxylated products so obtained;

Part 3 will be concerned with the nature of the products obtained by oxypropylation in light of the fact that certain side reactions invariably and inevitably occur,

- and Part 4 will be concerned with certain derivatives which can be obtained from these acidic esters and which, in turn, are valuable for a variety of purposes.

PART 1 Oxypropylations are conducted under a wide variety of conditions, not only in regard to presence or absence of catalyst, and the kind of catalyst, but also in regard to the time of reaction, temperature of reaction, speed of reaction, pressure during reaction, etc. For instance, oxyalkylations can be conducted at temperatures up to approximately 200 C. with pressures in about the same range up to about 200 pounds per square inch. They can be conducted also at temperatures approximating the boiling point of water or slightly above, as for example to C. Under such circumstances the pressure will be less than 30 pounds per square inch unless some special procedure is employed as is sometimes the case, to wit, keeping an atmosphere of inert gas such as nitrogen in the vessel during the reaction. Such lowtemperature-low reaction rate oxypropylations have been described very completely in U. S. Patent No. 2,448,664, to H. R. Fife, et al., dated September 7, 1948. Low ternperature, low pressure oxypropylations are particularly Example 1a The particular autoclave employed was one with a capacity of approximately gallons or on the average of about 125 pounds of reaction mass. The speed of the stirrer could be varied from 150 to 350 R. P. M. The initial charge was pounds of Armeen 12. This material according to Armour Chemical Company, is 90% dodecylamine, 9% tetradecylarnine and 1% Octadecenylamine. Even though this reagent itself is alkaline, 0.9 pounds of caustic soda were added. The reaction pot was flushed out with nitrogen, the autoclave sealed, and the automatic devices adjusted for injecting 75.2 pounds of propylene oxide in a 7.5-hour period. The pressure regulator was set for a maximum of -37 pounds per square inch. However, in this particular step and in all succeeding steps the pressure rarely got this high. In fact, the bulk of the reaction could take place, and probably did take place, at an appreciably lower pressure. This comparatively low pressure was the result of the fact that the reactant per se was basic and also because considerable catalyst was added. The propylene oxide 2a, preceding, equivalent to 14.95 pounds of the polyamine, 65.5 pounds of propylene oxide, and .47 pound of caustic soda, were subjected to further oxypropylation in the same manner described in the two preceding examples. The amount of propylene oxide added was 28.1 pounds. The conditions of reaction were the same as in the preceding example and the time period was approximately the same, to wit, 5 hours. The addition of the oxide was at a somewhat slower rate, being about 6 pounds per hour. When the reaction was complete part of the sample with withdrawn and the remainder subjected to further oxypropylation as described in Example 4a, immediately following.

Example 4a 70 pounds of reaction mass identified as Example 3a, preceding, and equivalent to 9.6 pounds of polyamine, 60.2 pounds of propylene oxide and .3 pound of caustic soda were subjected to further oxypropylation with 60.2 pounds of propylene oxide. The conditions as far as temperature and pressure were concerned were the same as in the previous example. The time period was 11 TABLE I Composition Before Composition After M M ax. ax. Ex. No. g a OK No. Temp., Pres, 2

e, Oxide, Catalyst, Amine, Oxide, Catalyst, C. p. s. i. lbs. lbs. lbs. lbs. lbs. lbs.

was added rather slowly at the rate of about 10 pounds per hour and, more important, the selected temperature was within the range of 220225 F. (somewhat higher than the boiling point of water). The initial introduction of propylene oxide was not starated until the heating devices had raised the temperature to approximately the boiling point of water. At the completion of the reaction a sample was taken and oxypropylation proceeded as in Example 2a, immediately following.

Example 2a 70 pounds of reaction mass identified as Example 1a, preceding, and equivalent to 19.75 parts of the amine, 49.5 parts of propylene oxide, and .59 part of caustic soda were subjected to reaction with 37.1 pounds of propylene oxide. The oxypropylation was conducted in substantially the same manner in regard to temperature and pressure as in Example In, preceding. The time period was shorter, to wit, 4.5 hours. The oxide was added at the rate of about 8 pounds per hour. At the end of the reaction period part of the sample was withdrawn and subjected to further oxypropylation as described in Example 3a, following.

Example 3a 80 pounds of the reaction mass identified as Example hours and the addition rate was at the rate of approximately 5.5 pounds per hour.

The following substances are shown in the above table of oxypropylations:

Examples 1a4a.Armeen 12. According to Armour Examples 5a-8a.-Armeen 18. According to Armour Chemical Company this material consists of:

Per cent Hexadecyl amine 6 Octadecyl amine 93 Octadecenyl amine 1 Examples 9a-12a.-Duomeen T. According to Armour Chemical Company this material consists of:

where R consists of straight chain radicals which are 16 and 18 carbon atoms in length.

Examples J3a16a.-Butyl cyclohexylamine.

Examples ]7a20a.Armeen 2C. According to Armour Chemical Company this material consists of:

Per cent Secondary octyl amine 8 Secondary decyl amine 9 Secondary dodecyl amine 47 Secondary tetradecyl amine 18 Secondary hexadecyl amine 8 Secondary octadecyl amine Examples 21a24a.-Reaction product of 1 mol Armeen with 1 mol glycidol.

The final product, i. e., at the end of the oxypropylation step, was apt to be either a straw color, or sometimes it would have a definite dark amber to amber-reddish tinge;

At all stages the materials were oil-soluble, that is, xyleneand kerosene-soluble. They were, of course, alkaline due in part to the residual caustic soda employed and due to their own inherent nature. At all stages they retained a very faint amine-like odor. Naturally this odor tended to become fainter as oxypropylation proceeded.

PART 2 As previously pointed out the present invention is concerned with acidic esters obtained from the oxypropylated derivatives described in Part 1, immediately preceding, and polycarboxy acids, particularly tricarboxy acids like citric and dicarboxy acids such as adipic acid, phthalic acid, or anhydride, succinic acid, diglycollic acid, sebacic acid, azelaic acid, aconitic acid, maleic acid or anhydride, citraconic acid or anhydride, maleic acid or anhydride adducts as obtained by the Diels-Alder reaction from products such as maleic anhydride, and cyclopentadiene. Such acids should be heat stable so they are not decomposed during esterification. They may contain as many as 36 carbon atoms as, for example, the acids obtained by dimerization of unsaturated fatty acids, unsaturated monocarboxy fatty acids, or unsaturated monocarboxy acids having 18 carbon atoms. Reference to the acid in the hereto appended claims obviously includes the anhydrides or any other obvious equivalents. My preference, however, is to use polycarboxy acids having not over 8 carbon atoms.

The production of esters including acid esters (fractional esters) from polycarboxy acids and glycols or other hydroxylated compounds is well known. Needless to say, various compounds may be used such as the low molal ester, the anhydride, the acyl chloride, etc. However, for purpose of economy it is customary to use either the acid or the anhydride. A conventional procedure is employed. On a laboratory scale one can employ a resin pot of the kind described in U. S. Patent No. 2,499,370, dated March 7, 1950 to DeGroote & Keiser, and particularly with one more opening to permit the use of a porous spreader if hydrochloric acid gas is to be used as a catalyst. Such device or absorption spreader consists of minute alundum thimbles which are connected to a glass tube. One can add a sulfonic acid such as paratoluene sulfonic acid as a catalyst. There is some objection to this because in some instances there is some evidence that this acid catalyst tends to decompose or rearrange heat-oxypropylated compounds, and particularly likely to do so if the esterification temperature is too high. In the case of polycarboxy acids such as diglycollic acid, which is strongly acidic there is no need to add any catalyst. The use of hydrochloric acid gas has one advantage over paratoluene sulfonic acid and that is that at the end of the reaction it can be removed by flushing out with nitrogen, whereas there is no reasonably convenient means available of removing the paratoluene sulfonic acid or other sulfonic acid employed. If hydrochloric acid is employed one need only pass the gas through at an exceedingly slow rate so as to keep the reaction mass acidic. Only a trace of acid need be present. I have employed hydrochloric acid gas or the aqueous acid itself to eliminate the initial basic material. My preference, however, is to use no catalyst whatsoever.

The products obtained in Part 1 preceding may contain a basic catalyst. As a general procedure I have added an amount of half-concentrated hydrochloric acid considerably in excess of what is required to neutralize the residual catalyst. The mixture is shaken thoroughly and allowed to stand overnight. It is then filtered and refluxed with the xylene present until the water can be separated in a phase-separating trap. As soon as the product is substantially free from water the distillation stops. This preliminary step can be carried out in the flask to be used for esterification. If there is any further deposition of sodium chloride during the reflux stage needless to say a second filtration may be required. In any event the neutral or slightly acidic solution of the oxypropylated derivatives described in Part 1 is then diluted further with sufficient xylene, decalin, petroleum solvent, or the like, so that one has obtained approximately a 40% solution. To this solution there is added a polycarboxylated reactant as previously described, such as phthalic anhydride, succinic acid or anhydride, diglycolic acid, etc. The mixture is refluxed until esterification is complete as indicated by elimination of water or drop in carboxyl value. Needless to say, if one produces a half-ester from an anhydride such as phthalic anhydride, no water is eliminated. However, if it is obtained from diglycolic acid, for example, water is eliminated. All such procedures are conventional and have been so thoroughly described in the literature that further consideration will be limited to a few examples and a comprehensive table.

I have preferred to use the following procedure: I have employed about 200 grams of the polyhydroxylated compound as described in Part 1, preceding; I have added about grams of benzene, and then refluxed this mixture in the glass resin pot using a phase-separating trap until the benzene carried out all the water present as water of solution or the equivalent. Ordinarily this refluxing temperature is apt to be in the neighborhood of to possibly C. When all this water or moisture has been removed I also withdraw approximately 20 grams or a little less benzene and then add the required amount of the carboxy reactant and also about 150 grams of a high boiling aromatic petroleum solvent.

After this material is added, refluxing is continued and, of course, is at a higher temperature, to wit, about to C. If the carboxy reactant is an anhydride needless to say no water of reaction appears; if the carboxy reactant is an acid, water of reaction should appear and should be eliminated at the above reaction temperature. if it is not eliminated I simply separate out another 10 or 20 cc. of benzene by means of the phase-separating trap and thus raise the temperature to or C., or even to 200 C., if need be. My preference is not to go above 200 C.

The use of such solvent is extremely satisfactory provicled one does not attempt to remove the solvent subsequently except by vacuum distillation and provided there is no objection to a little residue. Actually, when these materials are used for a purpose such as demulsification the solvent might just as well be allowed to remain. If the solvent is to be removed by distillation, and particularly vacuum distillation, then the high boiling aromatic petroleum solvent might well be replaced by some more expensive solvent, such as decalin or an alkylated decalin which has a rather definite or close range boiling point.

9 The removal of the solvent, of course, is purely a conventional procedure and requires no elaboration.

iii

propylati on' taking place, for example, at the primary alcohol radical or the secondary alcohol radical. Actual- TABLE II Amt Amount Ex. N

' Theo. Hydroxy Poly- Hydroxy Hydroxyl Polycarboxy Ex. No. Molec. Comcarboxy 33 5 Wt. Value pound, Reactant Reactp grams ant 1a 649 177 150 Diglycolic acid 63. 4 1a 649 177 150 Phthalic Anhydride 70.0 M 549 177 150 59.5 111 049 177 150 82.3 211 997 113 150 40.5 2a 997 113 150 44.0 2a 997 113 150 38.0 2a 997 113 150 52.6 3a 1, 345 83 150 Diglycolic acid 29. 7 3a 1, 345 33 150 Phthalic Anhydride 32. 8 3a 1,345 83 150 Oxalic aci 27.9 3a 1,345 83 150 38.6 4a 2, 505 72 150 25. 8 4a 2, 505 72 150 28. 4 411 2,505 72 150 24.2 411 2, 505 72 150 Aconitic acid 33. 5

TABLE III ly, when such products are obtained, such as a high molalpolypropylene glycol or the products obtained in the Time of Max Water manner herein described one does not obtain a single Ex NO, solvent @533: g g? gf o derivative such as HO(RO)72H or -(RO)nH in which n hm has one and only one value, for instance, 14, 15 or 16, or the like. Rather, one obtains a cogeneric mixture of 205 6 180 3 5 closely related or touching homologues. These materials g2 2 $8 3O invariably have high molecular weights and cannot be 224 7 180 separated from one another by any known procedure 132 2 8 without decomposition. The properties of such mixture 172 5 180 "if represent the contribution of the various individual memtgg 3 3 2% bers of the mixture. On a statistical basis, of course, it 183 5 130 35 can be appropriately specified. $2 2 $8 13 Simply by way of illustration reference is made to 172 7 180 1 U. S. Patent No. 2,549,434 dated April 17, 1951, to 178 7 180 De Groote et al. 154 7 180 10.4 180 8 180 5 The significant fact in regard to the oxypropylated poly- 40 amines herein described is that in the initial stage they The solvent employed, if any, can be removed from are substantially all water-insoluble, for instance, up to the finished ester by distillation and particularly vacuum a molecular g pf 00 or thereabouts. Actually, distillation. The final products or liquids are generally 9 molefular Welght represent a mixture of some pale amber to dark amber in color, and show moderate hlgher welghjl molecular mammal? and some lower viscosityv They can be bleached with bleaching clays, molecular we1ght materials. The higher ones are probfilten-ng chars and the Elm However, for the Purpose ably WBIEI-IDSOhIbIC. The product may tend to emulsify of demulsification or the like 60101. is not a factor and or disperse somewhat because some of the const1tuents, decolorization is not iusfified. being a cogeneric mixture, are water-soluble but the bulk In the above instance I have permitted the Solvents to are insoluble. Thus one gets emulsifiability or dispersibilremain Present in the final reaction mass. In other ity as noted. Such products are invariably xylene-soluble stances I have followed the same procedure using decalin or a mixture of decalin or benzene in the same manner and ultimately removed all the solvents by vacuum distillation. Appearances of the final products are much the same as the poly-ols before esterification and in some instances were somewhat darker in color and had a reddish cast and perhaps were somewhat more viscous.

PART 3 The oxypropylation derivatives previously described are obtained from two classes of amines, i. e., one class in which there is only one point of reactivity towards propylene oxide and a second class where there are two or more points of reactivity towards propylene oxide. My preference by far is to use the type where there are two or more points of reactivity towards propylene oxide. This is illustrated by examples elsewhere in the text, such as primary amines, various polyamines, secondary amines in which there is a hydroxyl radical in what is essentially the hydrocarbon part of the molecule, and particularly secondary amines which have been reacted with one or more moles of glycide so that there are at least two or more labile hydrogen atoms attached to oxygen present in the molecule.

Usually no effort is made to difierentiate between oxyregardless of whether the original reactants were or not. Reference is made to what has been said previously in regard to kerosene-solubility. For example, when the theoretical molecular weight gets somewhere past 4,000 or at approximately 5,000 the product is kerosene-soluble and water-insoluble. These kerosene-soluble oxyalkylation products are most desirable for preparing the esters. I have prepared hydroxylated compounds not only up to the theoretical molecular weight shown previously, i. e., about 8,000 but some which were much higher. I have prepared them, not only from diethylenetn'amine, but also from oxyethylated or oxybutylated derivatives previously referred to. The exact composition is open to question for reasons which are common to all oxyalkylations. It is interesting to note, however, that the molecular weights based on hydroxyl determinations at this point were considerably less, in the neighborhood of a third or a fourth of the value at maximum point. Referriug again to previous data it is to be noted, however, that over the range shown of kerosene-solubility the hydroxyl molecular weight has invariably stayed at twothirds or five-eights of the theoretical molecular weight.

It becomes obvious when carboxylic esters are prepared from such high molecular weight materials that the ultimate esterification product again must be a cogeneric mixture. Likewise, it is obvious that the contribution to the total molecular weight made by the polycarboxy acid is small. By the same token one would expect the effectiveness of the demulsifier to be comparable to the unesterified hydroxylated material. Remarkably enough, in many instances the product is distinctly better.

PART 4 As pointed out previously the final product obtained is a fractional ester having free carboxyl radicals. Such product can be used as an intermediate for conversion into other derivatives which are effective for various purposes, such as the breaking of petroleum emulsions of the kind herein described. For instance, such product can be neutralized with an amine so as to increase its water-solubility such as triethanolamine, tripropanolamine, oxyethylated tricthanolamine, etc. Similarly such product can be neutralized with some amine which tends to reduce the water-solubility such as cyclohexylamine, benzylamine, decylamine, tetra-decylamine, octadecylamine, etc. Furthermore, the residual carboxyl radicals can be esterified with alcohols, such as low molal alcohols, methyl, ethyl, propyl, butyl, etc., and also high molal alcohols, such as octyl, decyl, cyclohexanol, benzyl alcohol, octadecyl alcohol, etc. Such products are also valuable for a variety of purposes due to their modified solubility. This is particularly true where surface-active materials are of value and especially in demulsification of water-in-oil emulsions.

Having thus described my invention, what I claim as new and desire to obtain by Letters Patent, is

l. Hydrophile synthetic products; said hydrophile synthetic products being obtained by reaction between (A) a polycarboxy acid selected from the group consisting of acyclic and isocyclic acids having no more than 8 carbon atoms and consisting of carbon, hydrogen and oxygen, and (B) high molal oxypropylation derivatives of alkyl mono amines having present at least one group in which there is present at least 8 and not more than 32 carbon atoms joined by carbon to carbon linkages, with the proviso that (a) the initial amine be xylene-soluble; (b) the amount of propylene oxide employed be not less than 4 and not over 20 moles per reactive hydrogen atom present in the original amine, including reactive hydrogen atoms attached to oxygen atoms; (0) the oxypropylation product must be xylene-soluble; and with the further proviso that the ratio of (A) to (B) be one mole of (A) for each hydroxyl radical present in (B).

2. Hydrophile synthetic products; said hydrophile synthetic products being obtained by reaction between (A) a polycarboxy acid selected from the group consisting of acyclic and isocyclic acids having no more than 8 carbon atoms and consisting of carbon, hydrogen and oxygen, and (B) high molal oxypropylation derivatives of an alkyl mono amine having present at least 1 alkyl radical which in turn has at least 8 and not more than 32 carbon atoms joined by carbon to carbon linkages; and with the additional proviso that said amine contains at least 2 hydrogen atoms each attached to an oxygen atom as part of the molecule; with the further proviso that (a) the initial amine be xylene-soluble; (b) the amount of propylene oxide employed be not less than 4 and not over 20 moles per reactive hydrogen atom present in the original amine, including reactive hydrogen atoms attached to oxygen atoms; (a) the oxypropylation product must be xylene-soluble; and with the final proviso that the ratio of (A) to (B) be one mole of (A) for each hydroxyl radical present in (B 3. Hydrophile synthetic products; said hydrophile synthetic products being obtained by reaction between (A) a polycarboxy acid selected from the group consisting of acyclic and isocyclic acids having no more than 8 carbon atoms and consisting of carbon, hydrogen and oxygen, and (B) high molal oxypropylation derivatives of an alkyl mono amine having present at least 1 alkyl group which is the carbon-linked chain of a higher fatty acid and which in turn has at least 8 and not more than 22 carbon atoms; and with the additional proviso that said amine contains at least 2 hydrogen atoms each attached to an oxygen atom as part of the molecule; with the further proviso that (a) the initial amine be Xylene-soluble; (b) the amount of propylene oxide employed be not less than 4 and not over 20 moles per reactive hydrogen atom present in the original amine, including reactive hydrogen atoms attached to oxygen atoms; (0) the oxypropylation product must be xylene-soluble; and with the final proviso that the ratio of (A) to (B) be one mole of (A) for each hydroxyl radical present in (B).

4. Hydrophile synthetic products; said hydrophile synthetic products being obtained by reaction between (A) a polycarboxy acid selected from the group consisting of acyclic and isocyclic acids having no more than 8 carbon atoms and consisting of carbon, hydrogen and oxygen, and (B) high molal oxypropylation derivatives of an alkyl mono amine having present at least 1 alkyl group which is the carbon-linked chain of a higher fatty acid and which in turn has at least 8 and not more than 22 carbon atoms; and with the additional proviso that said amine contain at least 2 hydrogen atoms each attached to an oxygen atom as part of the molecule; said amine being derived by reaction involving at least one mole of glycide per mole of the corresponding percursory amine; with the further proviso that (a) the initial amine be xylene-soluble; (b) the amount of propylene oxide employed be not J less than 4 and not over 20 moles per reactive hydrogen atom present in the original amine, including reactive hydrogen atoms attached to oxygen atoms; (0) the oxypropylation product must be xylene-soluble; and with the final proviso that the ratio of (A) to (B) be one mole of (A) for each hydroxyl radical present in (B).

5. Hydrophile synthetic products; said hydrophile synthetic products being obtained by reaction between (A) a polycarboxy acid selected from the group consisting of acyclic and isocyclic acids having no more than 8 carbon atoms and consisting of carbon, hydrogen and oxygen, and (B) high molal oxypropylation derivatives of an alkyl mono amine having present 2 alkyl groups which are the carbon-linked chains of a higher fatty acid and, which in turn have at least 8 and not more than 22 carbon atoms; and with the additional proviso that said amine contains at least 2 hydrogen atoms each attached to an oxygen atom as part of the molecule; said amine being derived by reaction involving one mole of glycide per mole of the corresponding precursory secondary amine, with the further proviso that (a) the initial amine be xylene-soluble; (b) the amount of propylene oxide employed be not less than 4 and not over 20 moles per reactive hydrogen atom present in the original amine, ineluding reactive hydrogen atoms attached to oxygen atoms; (c) the oxypropylation product must be xylenesoluble, and with the final proviso that the ratio of (A) to (B) be one mole of (A) for each liydroxy radical present in (B).

6. Hydrophile synthetic products; said hydrophile synthetic products being obtained by reaction between (A) a dicarboxy acid selected from the group consisting of acyclic and isocyclic acids having no more than 8 carbon atoms and consisting of carbon, hydrogen and oxygen, and (B) high molal oxypropylation derivatives of an alkyl mono amine having present 2 alkyl groups which are the carbon-linked chains of a higher fatty acid and which in turn have at least 8 and not more than 22 carbon atoms; and with the additional proviso that said secondary amine contains at least 2 hydrogen atoms each attached to an oxygen atom as part of the molecule; said amine being derived by reaction involving one mole of glycide per mole of the corresponding precursory secondary amine; with the further proviso that (a) the initial amine be xylene-soluble; (b) the amount of propylene oxide employed be not less than 4 and not over 13 20 moles per reactive hydrogen atom present in the original amine, including reactive hydrogen atoms attached to an oxygen atom; (c) the oxypropylation product must be Xylene-soluble; and with the final proviso that the ratio of (A) to (B) be one mole of (A) for each hydroxy radical present in (B).

7. The product of claim 6 with the proviso that at least 16 and not more than 36 moles of propylene oxide be employed per mole of hydroxylated amine.

8. The product of claim 6 with the proviso that at least 16 and not more than 36 moles of propylene oxide be employed per mole of hydroxylated amine, and With the additional proviso that the dicarboxy acid is diglycolic acid.

9. The product of claim 6 with the proviso that at least 16 and not more than 36 moles of propylene oxide be employed per mole of hydroxylated amine, and with the additional proviso that the dicarboxy acid is phthalic anhydride.

10. The product of claim 6 with the proviso that at least 16 and not more than 36 moles of propylene oxide be employed per mole of hydroxylated amine, and with the additional proviso that the dicarboxy acid is oxalic acid.

11. The product of claim 6 with the proviso that at least 16 and not more than 36 moles of propylene oxide be employed per mole of hydroxylated amine, and with the additional proviso that the dicarboxy acid is aconitic acid.

12. The product of claim 6 with the proviso that at least 16 and not more than 36 moles of propylene oxide be employed per mole of hydroxylated amine, and with the additional proviso that the dicarboxy acid is citraconic acid.

No references cited. 

1. HYDROPHILE SYNTHETIC PRODUCTS; SAID HYDROPHILE SYNTHETIC PRODUCTS BEING OBTAINED BY REACTION BETWEEN (A) A POLYCARBOXYLIC ACID SELECTED FROM THE GROUP CONSISTING OF ACYCLIC AND ISOCYCLIC ACIDS HAVING NO MORE THAN 8 CARBON ATOMS AND CONSISTING OF CARBON, HYDROGEN AND OXYGEN, AND (B) HIGH MOLAL OXPROPYLATION DERIVATIVES OF ALKYL MONO AMINES HAVING PRESENT AT LEAST ONE GROUP IN WHICH THERE IS PRESENT AT LEAST 8 AND NOT MORE THAN 32 CARBON ATOMS JOINED BY CARBON TO CARBON LINKAGES, WITH THE PROVISO THAT (A) THE INITIAL AMINE BE XYLENE-SOLUBLE; (B) THE AMOUNT OF PROPYLENE OXIDE EMPLOYED BE NOT LESS THAN 4 AND NOT OVER 20 MOLES PER REACTIVE HYDROGEN PRESENT IN THE ORIGINAL AMINE, INCLUDING REACTIVE HYDROGEN ATOMS ATTACHED TO OXYGEN ATOMS; (C) THE OXYPROPYLATION PRODUCT MUST BE XYLENE-SOLUBLE; AND WITH THE FURTHER PROVISO THAT THE RATIO OF (A) TO (B) BE ONE MOLE OF (A) FOR EACH HYDROXYL RADICAL PRESENT IN (B). 